有机化学 ›› 2014, Vol. 34 ›› Issue (6): 1092-1103.DOI: 10.6023/cjoc201311044 上一篇    下一篇

综述与进展

氧化腈无铜点击反应构建氮氧杂环的研究进展

韩骞, 易超, 熊兴泉   

  1. 华侨大学材料科学与工程学院 福建省高校功能材料重点实验室 厦门 361021
  • 收稿日期:2013-11-26 修回日期:2014-01-11 出版日期:2014-06-25 发布日期:2014-02-10
  • 通讯作者: 熊兴泉 E-mail:xxqluli@hqu.edu.cn
  • 基金资助:

    国家自然科学基金(No. 21004024)、福建省自然科学基金(No. 2011J01046)、福建省“高校新世纪优秀人才支持计划”(No. 2012FJ-NCET-ZR03)、福建省“高校杰出青年科研人才培育计划”(No. 11FJPY02)以及“华侨大学中青年教师科研提升资助计划”(No. ZQN-YX103)资助项目.

Construction of Nitrogen-Oxygen-Heterocycles via Copper-Free Click Reactions of Nitrile Oxides

Han Qian, Yi Chao, Xiong Xingquan   

  1. College of Materials Science and Engineering, Huaqiao University, Key Laboratory for Functional Materials of Fujian Higher Education, Xiamen 361021
  • Received:2013-11-26 Revised:2014-01-11 Online:2014-06-25 Published:2014-02-10
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21004024), the Natural Science Foundation of Fujian Province (No. 2011J01046), the Program for New Century Excellent Talents in Fujian Province (No. 2012FJ-NCET-ZR03), the University Distinguished Young Research Talent Training Program of Fujian Province (No. 11FJPY02) and the Promotion Program for Young and Middle-aged Teacher in Science and Technology Research of Huaqiao University (No. ZQN-YX103).

点击化学(Click chemistry)自从2001年被Sharpless提出之后,得到了飞速的发展. 而Cu(I)催化的叠氮-炔之间的环加成(Cue-AAC)反应作为点击反应的典型代表,已广泛地应用于新材料的制备、药物的合成以及催化剂载体之中. 但是在反应过程中使用Cu(I)催化剂,导致产品易被金属铜盐污染,从而使该反应在生物医药等应用领域受到限制. 基于氧化腈的点击反应作为一类新型的点击反应,其不仅仅可以与炔、烯进行1,3-偶极环加成反应,还可以与腈反应. 由于该反应不需要铜金属催化以及有良好的立体选择性和区域选择性等的优点,常被应用于药物的制备以及一些特定结构生物活性化合物的合成中. 对基于氧化腈的点击反应最新进展进行综述.

关键词: 点击化学, 氧化腈, 炔, 烯, 腈, 无铜催化

Click chemistry has been developed rapidly, which was initially proposed by Sharpless and co-workers since 2001. As the representative of click chemistry, the Cu(I)-catalyzed azide-alkyne cycloaddition (Cue-AAC) reaction has been applied widely for the preparation of new materials, drugs and catalyst carriers. The copper metal contamination in the final products is a major concern because of the use of copper salts catalytic system. These drawbacks counteract their applications in the fields of biomedicine and pharmaceuticals. Click reactions based on nitrile oxides with the feature of copper-free catalysis, not only can produce isoxazoles and isoxazolines by reacting with nitrile oxides and alkynes/alkenes, but also can synthesize oxadiazoles from nitrile oxides and nitriles. Copper-free nitrile oxides click reactions have good region- and stereo-selective properties and have been applied to the synthesis of drugs and bioactive compounds with particular structures. The new progress of click reactions based on nitrile oxide is reviewed.

Key words: click chemistry, nitrile oxides, alkynes, alkenes, nitriles, copper-free catalysis